Oxide layers were prepared on Al-1050 substrates by an environmentally friendly plasma electrolytic oxidation process using an alkaline solution of Na2SiO3 (8 g/L) and NaOH (3 g/L) as the electrolyte. The effects of three different duty cycles (20%, 40%, and 60%) on the structure and hardness of the oxides were investigated. XRD analysis revealed that the oxides were mainly composed of α-Al2O3, γ-Al2O3, and mullite. The proportion of each phase depended on various electrical parameters, such as the duty cycle and frequency. The morphology, thickness, and the elemental distribution of the oxides were examined by scanning electron microscopy and energy dispersive spectroscopy. The thicknesses of the oxides were found to vary from 20 μm to more than 60 μm for various duty cycles, when identical treatment durations were used. The oxidation treatment also resulted in good adhesion between the oxide layer and the substrate. SEM images indicated that the oxide layers formed at the 60% duty cycle exhibited relatively coarser surfaces with larger pore sizes and sintering particles, and slower growth rates than did those formed at the 20% duty cycle, under identical treatment durations. The oxides prepared at the 20% duty cycle showed smooth surfaces. The oxides layers were found to improve the micro-hardness of Al-1050. In particular, the oxide layers formed at the 40% duty cycle exhibited relatively better micro-hardness owing to their compact microstructures.